Process for graft polymerization onto organic macromolecular materials

ABSTRACT

A process for graft polymerization of monomers onto organic macromolecular solid materials which comprises activating a macromolecular shaped article having a specific surface area of less than 3800 cm2/g with ozone under a condition of any point of the area defined by straight lines connecting p1, c1, c10, p10 in the attached FIG. 1, and further bringing said ozone activated material into contact with one or more radical polymerizable monomers in the presence of one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxyethyl ethylenediamine, pyridine, formamide and dimethyl formamide.

United States Patent Hosoda et al.

PROCESS FOR'GRAFT POLYMERIZATION ONTO ORGANIC MACROMOLECULAR MATERIALS Inventors: Kirokuro Hosoda, Yokohamashi; Yoshio Kadowaki, Tokyo; Eisiike Oda; Nobuo Hoshino, both of Yokohama-shi, all of J apan Assignee: The Furukawa Electric Company Limited, Chiyoda-ku, Tokyo, Japan Filed: Sept. 10, 1969 Appl. No.: 856,643

Foreign Application Priority Data Sept. 14, 1968 Japan ..43/66276 Oct. 19, 1968 Japan ..43/76215 US. Cl. ..117/47 A, 8/1 15.6, 117/106 R,

117/1388 A, 117/1388 E, 117/138.8 F, ll7/l38.8 N, 117/1388 UA, 260/230, 260/844, 260/859 PV, 260/862, 260/877, '260/878 R, 260/884 Int. Cl. ..B44d l/092, B44d 5/12 Field of Search..l 17/1 18, 47 A, 138.8 E, 106 R, 117/1388 A, 138.8 F, 138.8 N, 138.8 UA; 260/877, 844, 862, 8 78, 859 PV, 230, 884;

[56] References Cited UNITED STATES PATENTS 3,298,969 l/l967 DAlelio ..'....,260/877 3 ,487,037 12/1969 Michel .260/ 877 3,008,920 1 H1961 Urchick ..1 17/47 A 3,211,808 10/1965 Young et al. ..260/877 3,458,597 7/1969 Jabloner ..260/877 Primary Examiner-Alfred L. Leavitt Assistant Examiner-Janyce A. Bell Attorney-Wenderoth, Lind & Ponack [5 7] ABSTRACT A process for graft polymerization of monomers onto organic macromolecular solid materials which comprises activating a macromolecular shaped article having a specific surface area of less than 3800 cm /g with ozone under a condition of any point of the area defined by straight lines connecting p, c,, c p in the attached FIG. 1, and further bringing said ozone activated material into contact with one or more radical polymerizable monomers in the presence of one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxyethyl ethylenediamine, pyridine, formamide and dimethyl formamide.

21 Claims, 1 Drawing Figure Specific Surface Area of Organic Macromolecular Solid Material cm /g) KIROKURA HOSODA, YOSHIO KADOWAKI, EISUKE ODA and NOBUO HOSHINO,

INVEN'IOR.

[Mi BWMMLZQZM [\t tolfnoys PROCESS FOR GRAFT POLYMERIZATION ONTO ORGANIC MACROMOLECULAR MATERIALS The present invention relates to a process for improving the properties of organic macromolecular solid materials by giving new desired properties to them with substantially no sacrifice of their original properties.

Although many organic macromolecular solid materials have their inherent properties and are used for various purposes, demands for some additional properties have arisen as the uses of such materials have expanded.

Asa way of giving some new properties to a substrate of organic macromolecular solid materials, the common practice has been to blend an organic macromolecular material having such required properties with saidsubstrate. However this process has some limitations which are caused by the fact that the blending should be done in the molten state of said substrate and is not therefore applicable to any shaped substrates and that the compatibility of any macromolecular material with another is generally not good enough to give a new desired property to a sufficient degree without sacrificing its original good properties, e.g., a good processability and an excellent clarity. Recently the grafting process, which comprises graft polymerizing a desired monomer to a substrate of organic macromolecular materials, has been explored. The process has comparatively few limitations for various uses and is essentially suitable for giving new properties to said substrate. However, the methods of grafting hitherto known are technically difficult and neither economical norefficient since. the grafting reaction is activated by special ways using the ionizing radiation, the ultraviolet light, and the ultrasonic waves. I

On the other hand ozone grafting method, which may be one of the simplest grafting-methods, has been explored. However, it has been found that the oxidative deterioration and decomposition develop in said substrate during the activation of the substrate with ozone. Another difficulty in the ozone grafting process is that some homopolymerization accompanied the graft polymerization while the substrate activated with ozone is brought into contact with a monomer.

Those described above are practically important problems which are most disadvantageous for improvement of the properties of macromolecular materials; hence, at present the ozone grafting process is not used for practical purposes at all.

This invention is completed after an extensive study of the possible ways to give new desired properties to organic macromolecular solid materials with substantially no sacrifice of their original properties. The present invention shall be described in detail referring to the attached drawing, in which FIG. 1 is a graph specifyingthe condition of the ozone activation on triangular coordinates, under which organic macromolecular solid materials are brought into contact with ozone according to the present invention. 7

The objects of this invention are attained by bringing organic macromolecular solid materials having a specific surface area less than 3800 cm/ g into contact with ozone under a condition of any point of the area defined by the straight'lines connecting p,, c of p in FlG..1 to form active peroxides iirthe' surface layer of ethylenediamine, pyridine, formamide and dimethyl formamide in any phase to polymerize.

The reason why in this invention theconditions of the ozone activation are confined is that in such case that the grafting activity is given to said solid materials by the way of ozone treatment, the formation of the grafting activity proceeds at the rate related to the specific surface area and the surface temperature of the solid materials. When the surface to be brought into contact with ozone is at elevated temperature, a sufficient amount of active peroxides form in the surface layer of the solid material very rapidly, but, the socalled ozone deterioration proceeds also rapidly. The deterioration proceeds in the direction from the surface to the inner layer of the substrate, and the growing rate of the deterioration-is, at the initial stage of the ozone deterioration, governed also by the specific surface area and the surface temperature. Hence the appropriate conditions of the surface temperature and the period of the ozone activation are important in relation to the surface area of the substrate.

The inventors have found, after an extensive study of the conditions described above, that by bringing any of all organic macromolecular solid materials having a specific surface area of less than 3800 cmlginto contact with ozone under a condition of any point of the area defined by straight lines connecting p,, c,, c p in FIG. 1, while by selecting a proper activation time, depending on the degree of grafting desired, desirably under the maximum period given in FIG. 1 in which appropriate conditions of the ozone activation are given on triangular coordinates relating to the specific surface area of said solid materials, their surface tempera ture, and the period of the ozone activation, a desired degree of the grafting activity is given at substantially no sacrifice of their original properties.

The reason why the surface temperature is defined in the range between the points c, and c, in FIG. 1, viz. 60C and 200C, is based .on the new discovery that the formation ofthe grafting activity proceeds very rapidly as the result of occurrence of chain reaction like form ation of peroxides under those conditions and that the rate of the ozone deterioration at the temperature of 60C to 200C is, although, higher than the rates at a temperature below 60C, lowest as compared with the rate of. the formation of the grafting activity. Hence under the conditions of the ozone activation for the short time indicated in FIG. 1, the ozone deterioration of the substrate of organic macromolecular materials is negligibly light, and is limited to'the surface layer of the substrate; yet, a desired degree of the grafting activityis given to it.

Under 60C it-is impossible to avoid a serious deterioration which proceeds simultaneously with the peroxide formation if a sufficient amount of peroxides is to beobtained, since the deterioration develops in the or- .ganic macromolecular solid materials at approximately the same rate as theperoxide formation.

Above the surface temperature of 200C, however, the temperature of ozone also exceeds 200C and the danger of explosion increases; hence such dangerous conditions must be avoided as indicated in FIG. 1.

g The conditions on the line between the points p, and p in FlG. l have the meanings that it is very difficult to give a desired grafting activity onto the substrate of orsince the higher the temperature is the faster penetrates ozone into the substrate.

The upper-limitsof the period of the-ozone activation are such beyond which ozone diffuses deep into the substrate, thus causing a serious deterioration there, and the deterioration becomes remarkable since the rate of the formation of the grafting activity decreases with time.

According to the present invention, ozone may be present in the gas phase, e'.g., ozone-containing gas as manufactured industrially from air or oxygen, which is suitable for homogeneously treating the substrate of organic macromolecular materialsin complicated shape, or may be present in a liquid medium, which is suitable for giving a uniform temperature to the surface of the substrate, since the temperature affects the formation of the grafting activity considerably.

According to the present invention, the surface of the substrate is heated before beingbrought into contact with ozone, e.g., by preheating of the surface up to a desired temperature by a suitable heating means such as thermal conduction, thermal radiation, and high frequency induction heating. However, it is desirable to use ozone heated 60C to 200C as the surface reaches easily to the desired temperature without .preheating. The latter process is preferable since the substrate thus obtained is free from undesirable thermal history.

There is no particular limit to the concentration of ozone. However, it is preferable to use ozone of above 0.1 percent by volume to give a sufficient grafting activity in a short time, and it is also preferable to use the polyethylene is particularly high when the temperature isabove the dispersion temperature of polyethylene, and because at a temperature above its melting point the surface condition of polyethylene substrate varies greatly by melting, which in some cases, causes the decrease of the diffusion.

In case said organicmacromolecular material is highdensitypolyethylene, it is particularly preferable to bring it into contact with ozone at a temperature between 90 and 135C for the same reasons as above.

In case said organic macromolecular material is polypropylene it is particularly preferable to bring it into contact: with ozone at a temperature between 100175C for the same reasons as above.

' In case said organic macromolecular material is polyvinyl chloride it is particularly preferable to bring it into contact with ozone ata temperature between 87 to C, because the rate of the diffusion of ozone in polyvinyl chloride is particularly high at a temperature above its glass transition temperature and because above 150C there is a considerable deteriorationof polyvinyl chloride by a chain reaction 'of hydrogen chloride elimination.

For the grafting by bringing a substrate of organic macromolecular materials into contact with radical polymerizable monomers in the present invention, conventional grafting methods can be used. However, it is preferable to use said monomers in the gaseous state so as to control the rate of grafting, although an extraordinary high grafting activity is formed concentratedly in the surface of the substrate at the activation condition of the present invention. However, in case a large amount of organic macromolecular solid materials is to be treated, it is preferable to effect the grafting using said monomers in the liquid state so as to control the surface temperature, thus preventing the building-up of polymerization heat therein.

During the grafting described above, the presence in the reaction medium of one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxyethyl ethylenediamine, pyridine, formamide and dimethyl formamide has such effects as increasing the rate of grafting onto the surface layer of said shaped materials activated with ozone under the conditions of the present invention and suppressing homopolymer formation.

The process comprising an impregnation process, in which a substrate of organic macromolecular material is into contact with one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, 4 ethanolamine, hydroxyethyl ethylenediamine, pyridine, formamide and dimethyl formamide, and'a subsequent grafting process, in which the above treated substrate is brought into contact with radical polymerizable monomers, is particularly preferable, since the problem involved in separation of amines, amides, imines and imides and said monomers at the time ofrecovery thereof are eliminated.

After the grafting according to the present invention described above, desired properties such as dyeability, printability, adhesive property, antistatic property, and anti-slippery property, are given to the surface of any shaped articles made of organic macromolecular solid materials, and also excellent emulsion property, suspension property, and blending property are further given in case the solid materials have the shape such as powder, pellet, granule, flake, and chip.

Organic macromolecular solid materials for use in this patent are vinyl hydrocarbon polymers, vinyl polymers containing halogen atoms, vinyl polymers containing polar groups, and other synthetic addition polymers, polyamides, polyesters, polyimides, polysiloxanes, polysulfones, polyacetals, and other synthetic condensation, polymers, and natural polymers, such as low-density polyethylene, high densi ty polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyacrylonitrile, polyvinyl acetate, polymethyl methacrylate, polyvinyl carbazole,

polyvinylformal, polybutadiene, polyisoprene, polychloroprene, ethyleneipropylene copolymer,

ethylenepropylene-diene terpolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-vinyl acetate copolymer, vinyl chloridevinylacetate copolymer, vinyl chloride-propylene copolymer, styreneacrylonitrile copolymer, poly-ecaprolactam, polyhexamethylene adipamide, polyhexamethylene sebacate, polyundecamide, polyethylene flask and its content were heated at 120C for three minutes. After the graft reaction the homopolymer of the monomer occluded in the yarn was extracted by im mersing the yarn in acetone. The yarn was dried, weighed, and tested of various properties, viz. tensile strength, weather resistance (the period in which the tensile strength decreases to two thirds in a weatherometer), and dyeability with dispersion dyes. The results are shown in Table l Ozone treatment Graft reaction Concentration Tempera- Time Tempera- Time Weight Tensile Weather Dye- (vol. percent) ture 0.) (min.) ture 0.) (min.) increase strength resistanc ability (percent) (g./den.) (hi1) 3.1 120 0. 5 120 3 6. 4 3. 36 3, 100 Deep.

terephthalate, polyethylene isophthalate, polyo ximethylene, wood, paper, cotton, flaz, cellulose acetate, cellulose nitrate and other cellulose derivatives, natural rubber, wool, silk, starch, and a mixture of any two or more listed above.

The substrate of organic macromolecular materials may have the shape such as powder, pellet, granule, flake, chip, or any other given shape.

Radical polymerizable monomers for use in this invention to be brought into contact with organic macromolecular solid materials activated with ozone and to be polymerized as described above, are vinyl monomers, vinylidene monomers, and diene monomers, mixture of two or more of them, and also mixture of any one ormore of them with any one or more of radical copolymerizable monomers which are not polymerizable alone. Radical polymerizable monomers are such as styrene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, acrylic in Example 1 and in the following References the dyeability is evaluated in the order; deep medium pale very pale stained none.

it is obvious by comparing the results in Table l with the results in Table 2 in the following Reference 1, that the process of this invention is much better in improving the dyeability and the weather resistance and in retaining the tensile strength.

REFERENCE l TABLE 2 Ozone treatment Graft reaction Concentra- Weight Tensile Weather tion (vol. Tem era- Time Tcmpera- Time increase strength resistance Dyepercent) ture( C.) (min.) turc C.) (min.) (percent) (tn/den) r) ability 1 None 3. 3, 000 None. 2 3. 1 120 None 3. 30 2, 900 Stained. 3 3.1 26 None 3. 14 2, 400 Do. 4 3. 1 26 3 5.9 3.15 2,500 Pale NOTE: 1=control.

acid, methacrylic acid, methyl methacrylate, acryla- EXAMPLE 2 mide, vinyl pyridine, methyl vinylpyridine, vinyl pyrollidone, ethylene, butadiene, isoprene, and radical copolymerizable monomers are such as itaconic acid, maleic acid anhydride, crotonic acid, vinyl-iso-butyl ether, vinyl-trimethoxy silane, a-methyl styrene, propylene, butylene, all of which are particularly preferable to add to organic macromolecular solid materials dyeability, printability, adhesive property, antistatic property, and anti-slippery property,

1,540 cm lg) was treated at 120C for 0.5 minute with the gaseous ozone in oxygen, the concentration of which was 3.1 percent by volume. The yarn activated A high density polyethylene sheet of 1 mm in thickness (specific surface area; 25 cm lg) was treated at C for one minute with the gaseous ozone in oxgen, the concentration of which was 1.2 percent by volume. The sheet activated with ozone was placed in a glass flask together with an excess amount of methyl methacrylate monomer. The air in the flask was flushed out with nitrogen and then the flask and its content were heated at 80C for 60 minutes.

After the graft reaction the homopolymer of the monomer occluded in the sheet was extracted by immersing the sheet in acetone. The sheet was dried, weighed, and tested of an adhesive property as follows; a cellophane adhesive tape was compressed to the grafted surface of the sheet or to the surface which appeared by removing about 10 [.L-IhlCk grafted surface layer with a sand paper, and then the peel strength was measured by peeling the tape to the direction The results are shown in Table 3.

TABLE 3 Peel strength Ozone treatment Graft reaction (kg/cm.)

Concentra- Weight tion (vol. Tempera- Time Temoera- Time increase Grafted Inner percent) ture (/C.) (min.) ture (/C.) (min) (percent) surface region REFERENCE 2 The same high density polyethylene sheets as in Example 2 were given an ozone treatment as follows: (2) at 26C for 2 hours and (3) at 60C for 30 minutes.

Then methyl methacrylate was grafted onto the sheets (2) (3) under the same condition as in Example 2.

The grafted sheets thus obtained were weighed and tested of the adhesive property. The results are shown in Table 4.

I It is obvious that by increasing the time of ozone 10 treatment, the weight of the yarn increased, thus the graft polymerization proceeded with time, while the dyeability was much improved, however, at the longest ozone treatment, viz. fifteen minutes, which was made by way of an experiment for reference, the yarn was considerably deteriorated and its tensile strength was apparently decreased.

EXAMPLE 4 A low density polyethylene film of about 0.05 mm in thickness (specific surface area; 440 cm lg) was treated at 100C for 1 minute with the gaseous ozone in oxygen, the concentration of which was 0.9 percent by volume. The film activated with ozone was placed in a glass flask together with an excess amount of styrenemonoethanol amine solution. The air in the flask was flushed out with nitrogen and then the flask and its content were heated at 100C for 5 minutes (Experiment TABLE 4 Ozone treatment Graft reaction Peel stren th s/ m Conoentra- Temper- Temper- Weight tion (vol. ature Time ature Time increase Grafted Inner percent) 0.) (min) C.) (min.) (percent) surface region 1 None None 0. 47 0. 48 2 1. 2 26 120 80 60 8. 2 1.03 0. 96 3 1. 2 60 30 80 60 7. 4 1. 10 0. 85

NOTE: l=control.

EXAMPLE 3 The same polyethylene film as used above was A yarn of 6 denier polypropylene filaments (specific surface area; 1480 cm lg) was treated at 130C for various length of time with the gaseous ozone in oxygen, the concentration of which was 1.2 percent by volume. The yarn activated with ozone was placed in a glass flask and a gaseous mixture of acrylic acid, the partial pressure of which was 540 mmHg, and nitrogen was charged into it, and the flask and its contents were maintained at 180C for 10 minutes.

After the reaction above, the homopolymer of acrylic acid occluded in the yarn was extracted by immersing it in hot water. The yarn was dried, weighed, and tested of tensile strength and dyeability with basic dyes. The results are shown in Table 5.

treated at 26C for 1 hour with the same ozone as in Experiment l. The graft polymerization was effected also by the same procedure as in Experiment I at 100C for 15 minutes, except that pure styrene was used instead of the solution with monoethanol amine (Experiment 2).

After these experiments, the homopolymer of the monomer occluded in the films was extracted by immersing them in benzene. The films were dried and weighed. The results are shown in Table 6. Experiment 1 is a process of this invention and Experiment 2 is for reference. From Table 6 it is obvious that the process of 1 is much superior to the process of 2 in suppressing the homopolymerization.

TABLE 5 Ozone treatment Graft reaction Concentra- Temper- Temper Weight Tensile tron (vol. ature Time ature Time increase strength percent) C.) (min C.) (min.) (percent) (g./den.) Dyeability 1 None None 4. 61 None. 2 1. 2 130 0. 05 130 10 0. 05 4. 59 Very pale. 3 1. 2 130 0. 17 130 10 1. 5 4. 60 Medium. 4 1.2 2 130 10 11. 9 4. 71 Deep. 5 1.2 130 15 130 10 32.5 3 25 Do.

No'rE: 1=control; 2. 3 and 4=present invention; 5=for reference.

7 MW TABLE 6 F Ozone treatment Graft reaction Weight Weight Concentraincrease increase tion of mono by graft by homo- Coneentra- Temper- Temperethanolamine polymeripolymerition (vol. ature Time eture Time (vol. zation zation percent) C.) (min.) 0.) (min.) percent) (percent) (percent) 1 0. 9 100 1 100 3. 2 7. 5 0.7 2 0. 9 26 60 100 0 10. 1 6. 8

N o'rE: 1=present invention; 2=for reference.

' EXAMPLE 5 The same polyethylene films as in Example 4 were flask and its contents were heated at 110C for minutes.

After the reaction above, the homopolymer of butreated at 103C for 0.3 minute with the gaseous ozone 5 tadiene occluded in the film was extracted by imin oxygen, the concentration of which was 1.2 percent by volume.

One of the films activated with ozone was placed in a mersing it in cyclohexane. The filmwas dried, weighed, and tested of friction property by the method of ASTM D1894-63. The results are shown in Table 8.

ilitia 8 Ozone treatment Graft reaction Friction Concentra- Temper- Temper- Weight Tensile coefficient tion (vol. ature Time ature Time increase strength percent) 0.) (min.) C.) (min.) (percent) (kg/cm?) Static Dynamic None None 310 0.25 0.18 l. 2 120 2 110 20 14. U 310 0. 87 0. 4i) 1. 2 211 120 110 20 15. l 281 0. 8?. 0. 39

NOTE: 1=control; 2=present invention; 3=for reference.

glass flask together with .an excess amount of acrylic acid-dimethyl formamide solution, the concentration of the amide being 5 percent by volume. The air in the flask was flushed out with nitrogen and then the flask and its content were heated at 100C for 1 minute. (Experiment l) Acrylic acid was grafted onto another film at 103C for 10 minutes by the same procedure as in Experiment 1, except that pure acrylic acid was used instead of the solution with dimethyl formamide (Experiment 2).

After these experiments, the homopolymer of the monomer occluded in thefilm was extracted by immersing them in hot water. The films were dried and weighed. The results are shown in Table 7.

it is obvious from Table 8 that the grafted film by the process of this invention (Experiment 2) has a large friction coefficient, which means that anti-slippery property is given to the film.

ous mixture of ozone and oxygen the concentration of ozone being 0.9 percent by volume. The powder thus Ozone treatment Graft reaction Weight Coneentra- Weight inincrease tion of dicrease by by home- Concentra- Temper- Tempermethylgraft polypolymerition (vol. ature Time ature Time formamide merization zation percent) C.) (min.) C.) (min.) (vol. percent) (percent) (percent) 1 1. 2: 103 0. 3 100 1 5 10. 6 1. 2 2 1. 2 103 0. 3 100 10 0 8. 2 2. i)

N OTE: 1=present invention; 2=for reference.

Experiment 1 is a process of this invention and Experiment 2 is for a reference. From Table 7 it is obvious that the process of l is much superior to the process of 2 in suppressing the homopolymerization and in enhancing the graft polymerization.

EXAMPLE 6 activated with ozone was immersed in an excess amount of ethylacrylate in a glass flask. Then, after the air in the flask was flushed out with nitrogen, the flask andits content were heated at C for 10 minutes.

After the reaction above, the homopolymer of ethyl acrylate occluded in the powder was extracted by immersing it in acetone. The powder was dried, weighed, and after being compressed into 0.1mm thick film, tested of tensile strength and dyeability to dispersion dyes. The results are shown in Table 9.

it is obvious from Table 9 that polyethylene grafted by the process of this invention gains dyeability with no Sacrifice of its tensile strength.

- TABCLE. 9

Ozone treatment Graft reaction Concentra- Tempera- Tempera Weight Tensile tion (vol. ture Time ture Time increase strength Dyepereent) C.) (min) C.) (min.) (percent) (kgJcmJ) ability None None 197 None. 0. 100 14. 7 199 Deep. 60 100 10 13. 9 178 D0.

No'rE: 1=contr0l; 2=present invention; 3=for reference.

. 10 EXAMPLE 3 mersmg it in cyclohexanone. The powder was dried,

. weighed, and after being compressed into a 0.1 mm

The powder of high density polyethylene of 40u in thick-film, tested of the water permeability of moisture average diameter (specific. surface area; 156 cmlg) at 40C and at 90 percent of the relative humidity by was treated with ozone by the same way as in Example the cup method. The results are shown in Table 11.

aists 11 Ozone treatment Graft reaction Water permea- Concentra- Tempera- Tempera- Weight Tensile tion tion (vol. ture Time ture Time increase strength (g./m. percent) 0.) (mln.) 0.) (min.) (percent) (kg/cm?) mm./24 h.)

1 None None 197 15 2. 0. 5 100 3 100 37. 4 197 2. 8 3- 0. 5 26 00 100 I 20 36. 7 173 3. 1

NOTE: l=control; 2=present invention; 3=for reference.

7 at 120C for 1 minute. The powder thus treated with It is obvious from Table l 1 that the resistance of ozone was immersed in an excess amount of methyl polyethylene him against water vapor permeation is immethacryiate in a glass flask. Then after the air in the proved very much by grafting under the condition of flask was flushed out with nitrogen, the flask and its hi inv ntion.

content were heated at 120C for 30 minutes. 30

After the above reaction, the homopolymer of the EXAMPLE 1() monomer occluded in the powder was extracted by immersing it'in acetone. The powder was dried, weighed, Polypropylene tapes uniaxially drawn 800 percent, in and, after being compressed into 1 mm-thick film, a thickness of 0.01 mm (specific surfacejarea; 2230 tested of an adhesive property the Same way in cm lg) were treated at 150C for 0.3 m'inutewith the ample '2.The' results are shown in Table 10. gaseous ozone in oxygen, the concentration of which m a A .u rsgfiifi .7-

Ozone treatment Graft reaction Concentra- Tempera- Tempera- Weight Tensile Peel tion (vol. ture Time ture Time increase strength strength percent) 0.) (min) 0.) (min.) (percent (kg/cm!) (kg/cm.)

None None 310 0.51 1 120 an 28.3 310 1. 79 00 120 30 25. 9 292 1. 63

NOTE: 1=eontrol; 2=present invention; 3=for reference.

it is obvious from Table 10 that the adhesive properwas 1.2 percent by volume. Each tape thus activated ty of polyethylene grafted by the process of this invenwere fixed in a flask under some tension and grafted by tion is much better than that of original polyethylene. the same way as in Example 3 under the following condition; at 150C for 10 minutes using a gaseous mixture EXAMPLE 9 of acrylic acid (partial pressure; 510 mmHg) and The same polyethylene powder used in Example 7 nitrogen (Experiment 1) and at 150C for 2 minutes was treated at 100C for 3 minutes with ozone in a glass using the mixture of acrylic acid (partial pressure; 510 tube with a rectifying plate of sintered glass at its botmmi-ig), the vapor of dimethyl formamide (partial tom, under a fluidized condition in the gaseous mixture pressure; 56 mmHg) and nitrogen (Experiment 2). of ozone and oxygen. The concentration of ozone in After the reaction above, the homopolymer of the the mixture was 0.5 percent by volume. After the treatmonomer occluded in the tapes was extracted by imment, the gaseous mixture was flushed out with 60 mersing it in hot water. The tapes were dried and nitrogen, and then a gaseous mixture of vinylidene weighed. The results are shown in Table 12. chloride and nitrogen was charged into it. The tube and it is obvious from Table 12 that dimethyl formamide its content were heated at 100C for 20 minutes. presentin the reaction system has a remarkable effect After the reaction above, the homopolymer of the on enhancing the grafting and on suppressing the monomer occluded in the powder was extracted by imhomopolymerization.

Ozone treatment Graft reaction Partial Weight Weight Concentrapressure increase by increase by tion Temper- Temperof dimethyl graft polyhomopolyol. ature Time ature Tlme forrnarnide merization merization percent) C.) (min.) 0.) (min.) (mm. Hg) (percent) (percent) 1 1. 2 150 o. a 150 10 None 10. a 4. a

NOTE: 1 for reference; 2= present invention.

The adhesive strength of the surface of the film V V grafted by the procedure above, with rubber adhesives A biaxially stretched film of polyethylene terephthatimes greater than that ofthe 8"? fihh, late of 0.05 mm in thickness (specific surface area; 368 whlle the adhestfe strength of the Surface whlch P cmlg) was treated at 110C for 1 minute with the gasel Peated by l'ftmovlhg thehhout to I that grafted ous ozone in air, the concentration of which was 0.2 face tayef f a sand P P was hearty the Same as h percent by volume. The film activated with ozone was P the f f h h thatithe Process of h placed i a glass fl k together i an excess amount invention is suitable for giving an Improved adhesive of styrene monomer. The air in the flask was flushed P P tY the sufface layer, because the Ozone out with nitrogen and then the flask and its content act'vattoh only to thattayerwere heated at 90C for 1 hour. After the above reac- EXAMPLE 13 tion, the homopolymer of the monomer occluded in the film was extracted by immersing the film in benzene, The same polyethylene terephthalate film activated with ozone by the same procedure in Example 12 was The film was dried, weighed, and tested-of adhesive property-with rubber adhesives. The results are shown EXAMPLE 1 l in Table I3. l00C saturated vapor of acrylic acid was charged into TABLE 13 Ozone treatment Graft reaction Concentra- Temper- Temper- Weight Tensile Relative tion (vol. ature Time atur Time increase strength adhesive percent) C.) (min.) C.) (min.) (percent) (kg/cm!) strength 1 None None 2,100 1 2 0. 2 26 90 v 90 6O 0. 52 1, 940 1. Z 3 0. 2 110 1 90 60 0. 48 2,100 1. 5

placed in a glass flask and nitrogen gas containing the N out: 1 =control; 2=f0r reference; 3=present invention.

EXKMfiLE ii The same polyethylene terephthalate film as in Ex- .ample 11 was treated at l00C for 0.5 minutes with the gaseous ozone in oxygen, the concentration of which monomer occluded in the film was extracted by immersing it in hot water. The film was dried, and

weighed. The results are shown in Table 15.

was 0.9 percent by volume. The film activated with TABLE 15 Ozone treatment Graft reaction Concentra- Tempera- Tempera- Weight Tensile tion (vol. ture Time ture Time increase strength percent) 0.) (min.) 0.) (min.) (percent) (kg/cm!) Dyeabiiity 1 None None 2, 100 Stained.

0. 9 26 100 1. 7 1,950 Medium.

0. 9 100 0. 5 100 3 1. 9 2,100 Deep.

NOTE: 1=control; 2=for reference; 3=present invention.

Thus obtained film was deeply and homogeneously dyeable with basic dyes and dispersion dyes.

EXXMPLE 14 diameter (specific-surface area; cm lg) was treated at 100C for 0.3minute with ozone 0.9 percent by.

TABLE 14 Ozone treatment Graft reaction Concentra- Ter'npera- Tempera- Weight Tensile Relative tion (vol. ture Time ture Time increase I strength adhesive percent) 0.) (min.) 0.) (min.) (percent) (kg/cm!) strength 1 None None 2,100 2 0.9 2e 30 2.4 1,930 3 0. 9 100 0. 5 100 30 2. 6 2. 10 8 NOTE: 1=contro1; 2=for reference; 3=present invention.

a ate; .5; ei ytiii i ltierid of so, in average volume under the same fluidized condition as in Examessentially of one or more radical polymerizable pie 9. The powder activated with ozone was immersed monomers in the presence of one or more membersand dispersed in solution comprising; five parts of selected from the group consisting of trimethylamine, vinyltoluene, one part of divinylbenzene and four parts propylamine, ethylenediamine, piperidine, piperazine, of ethanol in a glass flask, then grafted at 60C for 1 5 morpholine, ethanolamine, hydroxy-ethyl hourafter the air in the flask was flushed out with ethylenediamine, pyridine, formamide and dimethyl nitrogen. formamide.

After the reaction above, the potsidmagwasiieaifii 2. A process as claimed in claim 1 wherein theozone ethanol, and then a small amount of plastsizer was is present in the gas phase.

added. By compression molding, clear sheets were ob- 3. A process as claimed in claim 1 wherein the ozone tained from the grafted powder impregnated with is present in a liquid medium. plastisizer, highly stable against heat distortion, sub- 4. A process as claimed in claim 1 wherein the ozone stantially above 170C. By the elemental analysis of is preheated to a temperature of between 60 and chlorine, it was found that the above sheets contained 0C- 5.2 percent by volume of the copolymer of styrene and 5. A process as claimedin claim 1 wherein the condivinylbenzene grafted onto polyvinyl chloride. The centration of the ozone is 0.1 to 10 percent by volume. results are shown in Table l6. 6. A process as claimed in claim 1 wherein the or- TABLE 10 V Ozone treatment Graft reaction Heat distortion Concentra- Temper- Temper- Weight temperature tion (vol. ature Time ature Time increase under load percent) C.) (min.) C.) (min.) (percent) (kg./mm. )(C.)

1 None None 135 2. 0.0 26 60 00 90 5. 2 145 3. 0. 9 100 0. 3 60 60 5. 2 170 NOTE: 1=eontroi; 2=for reference; 3=present invention.

EXAMPLE 15 ganic macromolecular shaped article is brought into contact with the monomer and simultaneously with one 30 or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxy-ethyl ethylenediamine, pyridine, formamide and dimethyl formamide.

The same polyvinyl chloride powder activated with ozone by the same procedure in Example 14 was grafted by the same way as in Example 14 under the following conditions; (i) at 50C for 1 hour using methyl methacrylate monomer of 30 percent concentration in methanol. (Experiment 1), (2) the same conditions as in Experiment 1, except that the powder was A Process as claimed in claim 1 wherein the impregnated, before the grafting process, with pyridine cal polymerizable monomer and one or more members by immersing them in 10 percent pyridine solution, selected from the group consisting of trimethylamine, ethanol (Experiment 2). The powder used in Experip y l t ethylenedlamlmf, piperidine, piperazine, ment 2 contains 0.4 percent by weight of pyridine after morpholllfei etllaflolammei y fy' y the impregnation treatment at 50C for 1 hour, and ethylenediamine, Py formamlde and dlmethyl ft drying in vacuo at formamide are in the gaseous state.

After the reaction the powder was washed in ethanol, 8. Kpio'a claimed in claim 1 wherein the radidried in vacuo, and weighed. The results are shown in cal polymerizable monomer and one or more members Table 17. selected from the group consisting of trimethylamine,

TABLE 17 v '7 '7 Ozone treatment I Graft reaction Concentra- Temper- Temper- Impregna- Weight tion (vol. nture Time ature Time tion of increase percent) C.) (min.) C.) (min.) pyridine (percent) 0.0 100 0.3 so No 4.4 I 0.9 100 0.3 so Yes 13.1

NOTE: 1 =for reference; 2=present invention.

is obvi ous from Table 17 that pyridine present in 55 propylamine, ethylenediamine, piperidine, piperazine,

the reaction system has a remarkable effect on enhancmorpholine, ethanolamine, hydroxy-ethyl ing the graftlngethylenediamine, pyridine, formamide and dimethyl What we claim is: formamide are in the liquid state. 1. A process for graft polymerization of monomers 9. A process as claimed in claim 1 wherein any one ontoorganic macromolecular solid materials, which 50 or more members selected from the group consisting of consists essentially of activating a macromolecular trimethylamine, propylamine, ethylenediamine,

solid material having a specific surface area of less than piperidine, piperazine, morpholine, ethanolamine, 3800 cm lg with ozone undera condition of any point hydroxy-ethyl ethylenediamine, pyridine, formamide of the area defined by the straight lines connecting p and dimethyl formamide are brought into contact with 0,, c p in FIG. 1 to produce ozone activated solid the organic macromolecular solid material prior to materials, and further bringing said ozone activated contactwith said monomer.

solid materials into contact with a material consisting 10. A process as claimed in claim 1 wherein the organic macromolecular solid material is preheated so as to heat the surface of the article to a temperature of between 60 and 200C.

1 l. A process as claimed in claim 1 wherein the radical polymerizable monomers are one or more members selected from the group consisting of styrene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, methyl methacrylate, acrylamide, vinylpyridine, methyl vinylpyridine, vinylpyrollidone, ethylene, butadiene and isoprene. v

12. A process as claimed in claim 1 wherein the or-' ganic macromolecular solid material is made of low density polyethylene and said low density polyethylene is brought into contact with ozone under a condition selected from any point within the area defined by the straight lines connecting p c c5, p, in FIG. 1.

13. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of high 20 density polyethylene and said high density polyethylene is brought into contact with ozone under a condition selected from any point within the area defined by the straight lines connecting p,,, c-,, p-, in FIG. 1.

14. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of polypropylene and said polypropylene is brought into contact with ozone under a condition selected from any point within the area defined by the straight lines connecting p c c,,, p, in FIG. 1.

15. A process as claimed in claim 1 wherein the orsynthetic addition polymer is selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride and polytetrafluoroethylene.

18. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of a synthetic condensation polymer.

19. A process as claimed in claim 18 wherein the condensation polymer is selected from the group consisting of polyethylene terephthalate, polyhexethy n dipa isi s p yr ap olactam- 20. A process as claimed in claim I- wherein the radical polymerizable monomers are mixed with radical copolymerizable monomers.

21. A process as claimed in claim 20 wherein the radical copolymerizable monomers to be mixed with radical polymerizable monomers are selected from the group consisting of itaconic acid, maleic acid anhydride, crotonic acid, vinyl-iso-butyl ether, vinyl-trimethoxy silane, a-methyl styrene, propylene and butylene. 

1. A process for graft polymerization of monomers onto organic macromolecular solid materials, which consists essentially of activating a macromolecular solid material having a specific surface area of less than 3800 cm2/g with ozone under a condition of any point of the area defined by the straight lines connecting p1, c1, c10, p10 in FIG. 1 to produce ozone activated solid materials, and further bringing said ozone activated solid materials into contact with a material consisting essentially of one or more radical polymerizable monomers in the presence of one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxy-ethyl ethylenediamine, pyridine, formamide and dimethyl formamide.
 2. A process as claimed in claim 1 wherein the ozone is present in the gas phase.
 3. A process as claimed in claim 1 wherein the ozone is present in a liquid medium.
 4. A process as claimed in claim 1 wherein the ozone is preheated to a temperature of between 60* and 200*C.
 5. A process as claimed in claim 1 wherein the concentration of the ozone is 0.1 to 10 percent by volume.
 6. A process as claimed in claim 1 wherein the organic macromolecular shaped article is brought into contact with the monomer and simultaneously with one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxy-ethyl ethylenediamine, pyridine, formamide and dimethyl formamide.
 7. A process as claimed in claim 1 wherein the radical polymerizable monomer and one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxy-ethyl ethylenediamine, pyridine, formamide and dimethyl formamide are in the gaseous state.
 8. A process as claimed in claim 1 wherein the radical polymerizable monomer and one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxy-ethyl ethylenediamine, pyridine, formamide and dimethyl formamide are in the liquid state.
 9. A process as claimed in claim 1 wherein any one or more members selected from the group consisting of trimethylamine, propylamine, ethylenediamine, piperidine, piperazine, morpholine, ethanolamine, hydroxy-ethyl ethylenediamine, pyridine, formamide and dimethyl formamide are brought into contact with the organic macromolecular solid material prior to contact with said monomer.
 10. A process as claimed in claim 1 wherein the organic macromolecular solid material is preheated so as to heat the surface of the article to a temperature of between 60* and 200*C.
 11. A process as claimed in claim 1 wherein the radical polymerizable monomers are one or more members selected from the group consisting of styrene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, methyl methacrylate, acrylamide, vinylpyridine, methyl vinylpyridine, vinylpyrollidone, ethylene, butadiene and isoprene.
 12. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of low density polyethylene and said low density polyethylene is brought into contact with ozone under a condition selected from any point within the area defined by the straight lines connecting p2, c2, c6, p6 in FIG.
 1. 13. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of high density polyethylene and said high density polyethylene is brought into contact with ozone under a condition selected from any point within the area defined by the straight lines connecting p4, c4, c7, p7 in FIG.
 1. 14. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of polypropylene and said polypropylene is brought into contact with ozone under a condition selected from any point within the area defined by the straight lines connecting p5, c5, c9, p9 in FIG.
 1. 15. A process as claimed in claim 1 wherEin the organic macromolecular solid material is made of polyvinyl chloride and said polyvinyl chloride is brought into contact with ozone under a condition selected from any point within the area defined by the straight lines connecting p3, c3, c8, p8 in FIG.
 1. 16. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of a synthetic addition polymer.
 17. A process as claimed in claim 16 wherein the synthetic addition polymer is selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride and polytetrafluoroethylene.
 18. A process as claimed in claim 1 wherein the organic macromolecular solid material is made of a synthetic condensation polymer.
 19. A process as claimed in claim 18 wherein the condensation polymer is selected from the group consisting of polyethylene terephthalate, polyhexamethylene adipamide and poly- epsilon -caprolactam.
 20. A process as claimed in claim 1 wherein the radical polymerizable monomers are mixed with radical copolymerizable monomers. 